WO2021227213A1 - Catalyst for use in removing antibiotics in water body by activating peroxymonosulfate, preparation method therefor, and application thereof - Google Patents

Abstract

A catalyst for use in removing antibiotics in a water body by activating peroxymonosulfate, a preparation method therefor, and an application thereof. The method comprises the following steps: mixing the catalyst with an antibiotic water body, stirring, adding peroxymonosulfate for a degradation reaction, and completing removal of antibiotics in the water body, wherein the catalyst is prepared by calcinating a waste lithium battery as a raw material, and the catalyst contains LiCoO₂ and Co₃O₄. Efficient degradation of the antibiotics in the water body can be realized by mixing a heterogeneous catalyst prepared by using the waste lithium battery as the raw material and peroxymonosulfate with an antibiotics-containing water body for the degradation reaction, and the present invention has the advantages of being easy to operate, low in treatment costs, wide in application range, high in treatment efficiency, good in treatment effect, high in reusability, environmentally friendly, etc., and good application value and application prospects.

Description

Catalyst for activating permonosulfate to remove antibiotics in water body and preparation method and application thereof Technical field

The invention belongs to the field of lithium battery recycling and advanced oxidation treatment of environmental pollutants, and relates to a method for removing antibiotics in water bodies, in particular to a catalyst for activating permonosulfate to remove antibiotics in water bodies and a preparation method thereof. application.

Background technique

With the continuous development of medicine and the increasing demand for medicines and other medical supplies, more and more pharmaceutical factories have emerged. Among the drugs produced, antibiotics are widely used to treat bacterial infections. However, in its production process, due to the improper management of the antibiotic-containing wastewater discharged by the factory, the wastewater is discharged into rivers and lakes, and then the pollutants are in the water. Accumulation in the environment causes harm to aquatic organisms. For example, levofloxacin hydrochloride is a typical fluoroquinolone antibiotic, which is widely used in the treatment of various respiratory and urinary tract diseases and skin infections. Its widespread use has led to an increase in bacterial resistance and ultimately endangers the environment and human health. Although the concentration of levofloxacin hydrochloride in natural wastewater is low, if the organic wastewater containing levofloxacin hydrochloride is discharged into rivers, lakes and oceans, it will seriously pollute the water body, which will have toxic effects on the microorganisms in the water body, and then kill the microorganisms. In addition, the stability of levofloxacin hydrochloride is extremely high, and it is difficult to achieve natural degradation of levofloxacin hydrochloride, which seriously endangers human health.

In view of the current status of antibiotic pollution in water bodies, many methods have been applied to remove antibiotics in water bodies, including microbial degradation, photo-Fenton oxidation, and biochar adsorption, but these methods have some drawbacks, such as complex process operations, secondary pollution, The cost is high, and when using microbial methods to degrade levofloxacin hydrochloride, levofloxacin hydrochloride can also inhibit the growth of bacteria. Therefore, finding a treatment method that can efficiently degrade antibiotics and is environmentally friendly is a major problem facing society today.

The advanced oxidation method is the most widely used in the field of water treatment. This method uses oxidants to react with organic pollutants in the water body, destroying the molecular structure of the pollutants, transforming them into other small molecules, and even completely mineralizing the pollutants to achieve the removal of pollutants. the goal of. The advanced oxidation technology based on peroxymonosulfate (PMS) is considered to be an efficient method to eliminate organic antibiotics. The sulfate radical (SO ₄ ^·- ) produced by peroxymonosulfate has higher oxidation Reduction potential, wider application range of pH value, stronger target pollutant selectivity, longer half-life, can mineralize organic pollutants in water to a higher degree. Since PMS is very stable at room temperature, the activator is the key to the PMS system, so many studies focus on the activation of PMS. Various activation methods (such as thermal method, ultraviolet irradiation method, ultrasonic method and catalytic activation method) are used for the activation of PMS. In these catalytic methods, transition metal ions (such as Co ²⁺ , Fe ²⁺ , Mn ^2+, etc.) are considered to be simple and efficient catalysts for activating PMS. However, the existing catalysts still have problems such as high preparation costs.

The widespread application of lithium-ion batteries will inevitably produce a large amount of harmful metal elements and flammable electrolyte, which is harmful to the environment and harmful to human health. Therefore, the recycling and reuse of used lithium batteries is particularly important. In recent years, in order to achieve the purpose of recycling and reuse, finding a suitable application for recycled materials has attracted widespread attention. Waste batteries can be used not only for the synthesis of new batteries, but also for the preparation of supercapacitors, oxygen evolution reactions, adsorption and photocatalysis and other functional materials. When most recycled materials are reused as functional materials, they need to undergo complex and expensive extraction and purification processes. Since the cathode materials of lithium batteries contain transition metal elements such as Co, Mn, and Ni, these elements are usually used to catalyze reactions. However, there are few reports on the use of lithium battery cathode materials as catalysts for the treatment of antibiotic wastewater.

Summary of the invention

The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a waste lithium battery preparation with simple operation, low processing cost, wide application range, high processing efficiency, good processing effect, strong reusability, and environment-friendly The catalyst is activated per monosulfate to remove antibiotics in the water.

In the actual research process of the present invention, it is found that if the cathode material recovered from the waste lithium battery is used to treat antibiotic wastewater, the following problems need to be overcome: (1) How to effectively recover the cathode material from the waste lithium battery; (2) How to Convert the recovered positive electrode material into a new catalyst suitable for activating PMS; (3) How to use the positive electrode material to activate PMS to achieve efficient treatment of antibiotic wastewater. Therefore, how to combine the recycling of waste lithium batteries with the treatment of antibiotic waste water is of great significance for realizing the purpose of degrading antibiotic waste water while recycling waste lithium batteries.

In order to solve the above technical problems, the technical solution adopted by the present invention is:

A method for removing antibiotics in water by activating permonosulfate using a catalyst prepared from spent lithium batteries, including the following steps: mixing the catalyst with antibiotic water, stirring, and adding permonosulfate for degradation reaction to complete the removal of antibiotics in water The catalyst is prepared by calcining waste lithium batteries as raw materials; the catalyst includes LiCoO ₂ and Co ₃ O ₄ .

The above method for removing antibiotics in water by activating permonosulfate by using a catalyst prepared from a waste lithium battery is further improved, and the _{mass percentage of LiCoO 2} in the catalyst is greater than or equal to 90%.

The above-mentioned method for activating permonosulfate to remove antibiotics in the water body by using a catalyst prepared from a waste lithium battery is further improved. The method for preparing the catalyst includes the following steps:

S1. Discharging, disassembling and separating the waste lithium battery to obtain the positive electrode material;

S2, calcining the positive electrode material obtained in step S1 to obtain a catalyst.

The above method for removing antibiotics in water by activating permonosulfate using a catalyst prepared from spent lithium batteries is further improved. In step S2, the calcination temperature is 550°C to 850°C; the calcination time ≥5 Hour.

The above method of using a catalyst prepared from a waste lithium battery to activate permonosulfate to remove antibiotics in a water body is further improved. In the step S1, the waste lithium battery is a waste mobile phone lithium battery.

The above method of using a catalyst prepared from spent lithium batteries to activate permonosulfate to remove antibiotics in water is further improved. The addition amount of the catalyst is 100 mg to 800 mg of catalyst per liter of antibiotic water; The addition amount is 0.3mmol-0.9mmol per liter of antibiotic water added permonosulfate.

The above method for removing antibiotics from the water body by activating permonosulfate using a catalyst prepared from a waste lithium battery is further improved. The antibiotics in the antibiotic water body include levofloxacin hydrochloride, ciprofloxacin, norfloxacin, tetracycline hydrochloride, and gold At least one of oxytetracycline and oxytetracycline.

The above method for removing antibiotics in water by activating permonosulfate using a catalyst prepared from spent lithium batteries is further improved. The concentration of the antibiotic in the antibiotic water is 100 μg/L-20 mg/L; the pH value of the antibiotic water For 3-11.

The above method of using a catalyst prepared from a waste lithium battery to activate permonosulfate to remove antibiotics in a water body is further improved, and the stirring time is 30 minutes to 60 minutes.

The above method of using a catalyst prepared from a waste lithium battery to activate permonosulfate to remove antibiotics in a water body is further improved, and the degradation reaction time is 40 minutes to 60 minutes.

Compared with the prior art, the advantages of the present invention are:

(1) The present invention provides a method for removing antibiotics from water by using a catalyst prepared from a waste lithium battery to activate permonosulfate, by combining a heterogeneous catalyst, permonosulfate and antibiotic-containing The water is mixed to carry out the degradation reaction, and the high-efficiency degradation of antibiotics in the water can be realized. Taking levofloxacin hydrochloride as an example, the principle of degradation of antibiotics in water is shown in formulas (1)～(14), specifically: divalent cobalt and permonosulfate undergo a series of reactions to produce SO ₄ ^·- , ·OH And · O ₂ ^- and other free radicals and ¹ O ₂ , these groups react with the pollutants adsorbed on the surface of the catalyst to degrade the antibiotic (levofloxacin hydrochloride) into small molecular substances, and finally degrade into water and carbon dioxide, thereby achieving Efficient degradation of levofloxacin hydrochloride. The method for removing antibiotics in the water body of the present invention can be carried out under normal temperature and pressure, can mineralize antibiotics (such as levofloxacin hydrochloride) into water and carbon dioxide, and can effectively separate solid and liquid without secondary pollution, and has simple operation and no need Large-scale equipment, low cost and other advantages, but also has a wide range of applications, high treatment efficiency, good treatment effect, strong reusability, environmentally friendly, can efficiently degrade antibiotics in water bodies, and has good application value and application prospects.

Co ²⁺ +HSO ₅ ^– →Co ³⁺ +SO ₄ ^·- +OH ^– (1)

Co ²⁺ +HSO ₅ ^– →Co ³⁺ +SO ₄ ^2- +·OH (2)

Co ³⁺ +HSO ₅ ^– →Co ²⁺ +SO ₅ ^·- +H ⁺ (3)

SO ₄ ^·- +OH ^– →SO ₄ ^2- +·OH (4)

SO ₄ ^·- +H ₂ O→SO ₄ ^2- +·OH+H ⁺ (5)

2SO ₅ ^·- +H ₂ O→2HSO ₄ ^– +1.5 ¹ O ₂ (6)

HSO ₅ ^– →SO ₅ ^2- +H ⁺ (7)

HSO ₅ ^– +SO ₅ ^2- →HSO ₄ ^– +SO ₄ ^2- + ¹ O ₂ (8)

HSO ₅ ^– +H ₂ O→HSO ₄ ^– +H ₂ O ₂ (9)

SO ₅ ^2- +H ₂ O→SO ₄ ^2- +H ₂ O ₂ (10)

H ₂ O ₂ →H ⁺ +HO ₂ ^·- (11)

_{^{HO 2 · - → H + +}} · O 2 - (12)

_{^{2 · O 2 - + 2H +}} → 1 O 2 + H 2 O 2 (13)

^{_{SO 4 · - / · OH /}} · O 2 - / 1 O 2 + LFX → Intermediate _{+ CO 2 + H 2 O (} 14)

(2) Compared with the catalyst prepared by the traditional method, the catalyst prepared by the present invention requires a wide range of sources of raw materials and is low in price, which is more in line with the standards of modern science and technology that are environmentally friendly and inexpensive. It can be seen that the catalyst of the present invention has a wide range of raw materials, economical and practical, and is a green, environmentally friendly and economical heterogeneous catalytic material.

(3) In the method of the present invention, the preparation method of the catalyst used uses waste lithium batteries as raw materials, and can be prepared by simple pretreatment and calcination to obtain a heterogeneous catalyst with high catalytic activity. Compared with other conventional methods, the preparation method of the present invention has the advantages of simple process, mild reaction conditions, convenient operation, clean and pollution-free, etc., is suitable for large-scale preparation, and is convenient for industrial use.

(4) In the method of the present invention, by optimizing the calcination conditions, the prepared heterogeneous catalyst has a rich layered structure, so the catalyst provides more active sites and multi-electron transfer during the reaction process, thereby improving the catalysis Active, this is because if the calcination temperature is too low, the PVDF binder and conductive carbon in the battery cathode material cannot be fully burned and removed; if the calcination temperature is too high, it is not conducive to the formation of layered LiCoO ₂ ; At the same time, if the calcination time is too short, the resulting catalyst is unstable, and the calcination time is too long will cause unnecessary energy consumption.

(5) In the method of the present invention, in the catalyst used, the repetitive utilization rate of the material is also another criterion for measuring its practical application. The catalyst of the present invention is continuously used to treat water containing levofloxacin hydrochloride for 4 times, and the catalytic effect is basically unchanged, still as high as 83%, which is maintained at a relatively high level. It can be seen that the catalyst of the present invention exhibits excellent stability, and after use The recovery method of the materials is relatively simple, and most of the materials can be obtained only by suction filtration, and the loss rate of materials is low. Therefore, the catalyst of the present invention has the advantages of good stability, strong reusability, simple recovery, high recovery rate, etc., and is a heterogeneous catalytic material with broad application prospects.

(6) In the present invention, the catalyst used can also exhibit high catalytic activity when degrading antibiotics (such as levofloxacin hydrochloride) in the presence of multiple anions and cations, and has a wide range of application prospects in the degradation of environmental pollutants.

(7) In the present invention, the catalyst used in the pH range of 3-11 degrades antibiotics (such as levofloxacin hydrochloride) can also exhibit higher catalytic activity, and has broad application prospects in the degradation of environmental pollutants.

(8) In the present invention, the catalyst used can efficiently degrade a variety of antibiotic pollutant wastewater, such as ciprofloxacin, norfloxacin, levofloxacin hydrochloride, tetracycline hydrochloride, chlortetracycline and oxytetracycline. In this reaction system, all of the above antibiotics can degrade more than 90%.

(9) In the present invention, the catalyst used in the actual water body (tap water, river water, lake water, medical wastewater) can still show higher catalytic activity, and in the high content of organic wastewater (20mg/L levofloxacin hydrochloride) and low content Organic wastewater (100μg/L levofloxacin hydrochloride) all worked well.

Description of the drawings

In order to make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely in conjunction with the accompanying drawings in the embodiments of the present invention.

Figure 1 is an SEM image of the catalyst (CM-850) prepared in Example 1 of the present invention.

Figure 2 is the XRD pattern of the catalyst (CM-650, CM-850) prepared in Example 1 of the present invention.

Figure 3 is a diagram showing the degradation effect of different catalysts on levofloxacin hydrochloride in Example 1 of the present invention.

Figure 4 is a graph showing the degradation effect of the catalyst in Example 2 of the present invention on levofloxacin hydrochloride solutions with different pH values.

Figure 5 is a diagram showing the degradation effect of the catalyst in Example 3 of the present invention on different antibiotic solutions.

Fig. 6 is a graph showing the degradation effect of the catalyst in Example 4 of the present invention on levofloxacin hydrochloride under different interference ion conditions.

Figure 7 is a graph showing the repeated degradation effect of the catalyst in Example 5 of the present invention on levofloxacin hydrochloride.

Fig. 8 is a graph showing the degradation effect of the catalyst in Example 6 of the present invention on levofloxacin hydrochloride in different concentrations and different water bodies.

Detailed ways

The following further describes the present invention with reference to the accompanying drawings of the specification and specific preferred embodiments, but the protection scope of the present invention is not limited thereby.

The materials and instruments used in the following examples are all commercially available. In the embodiments of the present invention, unless otherwise specified, the process used is a conventional process, the equipment used is a conventional equipment, and the data obtained is the average value of more than three tests.

Example 1

A method for removing antibiotics from water by using a catalyst prepared from spent lithium batteries to activate permonosulfate, specifically using a catalyst to remove levofloxacin hydrochloride in water, including the following steps: weighing the catalyst (CM-550, CM-650, CM- 750, CM-850 and Co ₃ O ₄ ), each 40mg, were added to 100mL, 10mg/L levofloxacin hydrochloride (LFX) solution (the pH value of the solution was 4.65), magnetically stirred for 30 minutes to reach adsorption equilibrium, add The degradation reaction of 0.05mmol permonosulfate (PMS) was carried out for 60 minutes to complete the treatment of antibiotics in the water.

No catalyst was added as a control group, only permonosulfate (PMS) was added, and other conditions were the same.

In Example 1, the preparation method of the catalysts (CM-550, CM-650, CM-750 and CM-850) used includes the following steps:

(1) After discharging (soaking and discharging in low-concentration NaCl salt water for 5 hours, take it out for natural air drying), dismantle (disassemble the battery in a fume hood, and separate the shell, positive electrode sheet, negative electrode sheet and other materials), and separate (After cutting the positive electrode sheet and soaking it in NaOH, stirring continuously with a glass rod, the aluminum foil will dissolve, and the positive electrode material attached to the aluminum foil will naturally fall off) and other pretreatment steps to obtain the positive electrode material.

(2) Heat the positive electrode material obtained in step (1) at a temperature increase rate of 5°C/min, and calcinate at a temperature of 550°C, 650°C, 750°C, and 850°C for 5 hours to obtain a catalyst. It contains 94% by mass of LiCoO ₂ , and the catalysts corresponding to calcination temperatures of 550°C, 650°C, 750°C, and 850°C are CM-550, CM-650, CM-750 and CM-850 in sequence.

In Example 1, _{the preparation method of the catalyst (Co 3} O ₄ ) used includes the following steps:

The preparation method of Co ₃ O _{4 : Mix CoCl 2} 6H ₂ O and NH ₄ HCO ₃ with a substance amount of 1:2 until the mixture is uniform. The mixture was then placed in a vacuum drying oven (80°C) to dry for 8 hours to obtain a pink precursor. The precursor was calcined in a muffle furnace (650°C) for 5 hours to obtain black Co ₃ O ₄ .

Figure 1 is an SEM image of the catalyst (CM-850) prepared in Example 1 of the present invention. It can be seen from Fig. 1 that the catalyst (CM-850) prepared by the present invention contains an obvious layered structure, which will provide more active sites and multi-electron transfer during the reaction process, thereby improving the catalytic activity.

Table 1 is the elemental composition of the catalyst (CM-850) prepared in Example 1 of the present invention

element	At%
Co	58.56
O	31.44
Li	6.68
Al	2.58
C	0.74

It can be seen from Table 1 that CM-850 contains five elements: cobalt, oxygen, lithium, aluminum, and carbon. Among them, the aluminum element comes from aluminum foil, and the carbon element comes from conductive carbon. Lithium is completely present in the form of lithium cobalt oxide, and the content of lithium cobalt oxide can be calculated from the percentage of lithium element.

Figure 2 is the XRD pattern of the catalyst (CM-650, CM-850) prepared in Example 1 of the present invention. Figure 2 shows, the peak catalyst of this invention (CM-650, CM-850 ) with LiCoO ₂ and Co ₃ O characteristic peak ₄ corresponds to the main catalyst of the present invention, the phase composition of LiCoO ₂ and Co ₃ O _4.

During the catalytic reaction, 4 mL was sampled every 10 minutes, and the obtained sample was placed in a 5 mL centrifuge tube through a 0.45 um filter membrane, and 0.1 mL of methanol quencher was added to terminate the reaction. The concentration of all samples was measured by ultraviolet at a wavelength of 292nm, and the degradation effects of different catalysts on levofloxacin hydrochloride under different degradation time conditions were obtained, as shown in Figure 3.

Figure 3 is a diagram showing the degradation effect of different catalysts on levofloxacin hydrochloride in Example 1 of the present invention. It can be seen from Figure 3 that the catalysts (CM-550, CM-650, CM-750 and CM-850) recovered and prepared at different calcination temperatures in the present invention have a degradation efficiency of 88% and 89% for levofloxacin hydrochloride after 60 minutes of degradation. , 89%, 94%, respectively, the degradation rate ^{0.03692min -1, 0.03754min -1, 0.03875min -1} , 0.05195min -1, can be seen, the present invention is prepared using lithium waste catalyst degradation efficiency were levofloxacin hydrochloride More than 88%, and CM-850 exhibits the best catalytic effect, which shows that the catalyst prepared by the present invention can effectively degrade levofloxacin hydrochloride in water and exhibits better catalytic performance.

In addition, when PMS was added alone, there was only 4.5% degradation. When the catalyst of the present invention is added alone as an adsorbent, less than 10% of levofloxacin hydrochloride is removed by adsorption. When used in combination with the catalyst of the present invention and PMS, the degradation rate of levofloxacin hydrochloride is greatly improved, indicating that the catalyst of the present invention can activate PMS. Thereby, the high-efficiency degradation of levofloxacin hydrochloride can be realized.

Implementation column 2

A method for removing antibiotics in water by using a catalyst prepared from spent lithium batteries to activate permonosulfate, specifically using a catalyst to remove levofloxacin hydrochloride in water, including the following steps: weighing 6 parts of the catalyst (CM-850), each 40mg, Add levofloxacin hydrochloride (LFX) solutions with pH values of 3, 4.65, 5, 7, 9, 11 respectively (the volume of these solutions is 100 mL, and the concentration is 10 mg/L), and magnetically stir for 30 minutes to reach adsorption equilibrium , Each add 0.05mmol permonosulfate (PMS) to carry out the degradation reaction for 60 minutes to complete the treatment of antibiotics in the water.

During the catalytic reaction, 4 mL was sampled every 10 minutes, and the obtained sample was placed in a 5 mL centrifuge tube through a 0.45 um filter membrane, and 0.1 mL of methanol quencher was added to terminate the reaction. The concentration of all samples was measured by ultraviolet at a wavelength of 292 nm, and the degradation effect of the catalyst of the present invention on the levofloxacin hydrochloride solution with different pH values was obtained, as shown in FIG. 4.

Figure 4 is a graph showing the degradation effect of the catalyst in Example 2 of the present invention on levofloxacin hydrochloride solutions with different pH values. It can be seen from Figure 4 that the degradation efficiency of the catalyst of the present invention (CM-850) on the levofloxacin hydrochloride solution with pH values of 3, 4.65, 5, 7, 9, and 11 after being degraded for 60 minutes are 91%, 94%, 92%, respectively. 92%, 93%, 47%. It can be seen that the suitable pH range of this system is 3-10, but when the pH rises to 11, the degradation reaction is inhibited. This is because at higher pH, PMS will pass through non-radical pathways. It decomposes itself into SO ₄ ^2- , O ₂ , and H ₂ O, thereby inhibiting the formation _{of the active group SO 4} ^·-. In addition, under alkaline conditions, the active group SO ₄ ^·- will react with OH ^- to generate ·OH (hydroxyl radical), but the hydroxyl radical will be quenched by the by-products produced by PMS self-decomposition, thereby reducing the degradation reaction s speed. The reaction that occurred is as follows:

_{^{HSO 5 - + OH - → SO}} 4 2- + O 2 + H 2 O (15)

SO ₄ ^·- +OH ^– →SO ₄ ^2- +·OH (16)

Implementation column 3

A method for removing antibiotics in water by using catalysts prepared from spent lithium batteries to activate permonosulfate, specifically using catalysts to remove multiple types of antibiotics in water, including the following steps: weighing 6 parts of the catalyst (CM-850), 40mg each were added to levofloxacin hydrochloride (LFX) solution, ciprofloxacin solution, norfloxacin solution, tetracycline hydrochloride solution, oxytetracycline solution, chlortetracycline solution (the volume of these solutions is 100mL, and the concentration is 10mg/L, pH value of 4.65), magnetic stirring for 30 minutes to reach adsorption equilibrium, each add 0.05mmol permonosulfate (PMS) for degradation reaction for 60 minutes to complete the treatment of antibiotics in the water.

During the catalytic reaction, 4 mL was sampled every 10 minutes, and the obtained sample was placed in a 5 mL centrifuge tube through a 0.45 um filter membrane, and 0.1 mL of methanol quencher was added to terminate the reaction. The concentration of all samples was measured by ultraviolet at a wavelength of 292 nm, and the degradation effect of the catalyst of the present invention on different antibiotic solutions was obtained, as shown in FIG. 5.

Figure 5 is a diagram showing the degradation effect of the catalyst in Example 3 of the present invention on different antibiotic solutions. It can be seen from Figure 5 that the catalyst of the present invention (CM-850) has a degradation efficiency of 94% and 92% for levofloxacin hydrochloride, ciprofloxacin, norfloxacin, tetracycline hydrochloride, oxytetracycline and chlortetracycline after 60 minutes of degradation. %, 95%, 93%, 93%, 91%. It can be seen that the system has good treatment effects on different antibiotic wastewater, and can efficiently degrade antibiotics such as levofloxacin hydrochloride, ciprofloxacin, norfloxacin, tetracycline hydrochloride, oxytetracycline and chlortetracycline.

Implementation column 4

The method of the present invention investigated the anti-interference performance, comprising the steps of: weighing 6 parts catalyst (CM-850), each of 40mg, were added to a solution containing ^{1mM K +, Mg 2+, Ca} 2+, Cl -, NO 3-, In SO ₄ ^2- levofloxacin hydrochloride (LFX) solution (the volume of these solutions is 100 mL, the concentration is 10 mg/L, and the pH value is 4.65), magnetically stir for 30 minutes to reach adsorption equilibrium, add 0.05 mmol for each Sulfate (PMS) undergoes a degradation reaction for 60 minutes to complete the treatment of antibiotics in the water body.

During the catalytic reaction, 4 mL was sampled every 10 minutes, and the obtained sample was placed in a 5 mL centrifuge tube through a 0.45 um filter membrane, and 0.1 mL of methanol quencher was added to terminate the reaction. The concentration of all samples was measured by ultraviolet at a wavelength of 292 nm, and the degradation effect of the catalyst of the present invention on levofloxacin hydrochloride under different interference ion conditions was obtained, as shown in FIG. 6.

Fig. 6 is a graph showing the degradation effect of the catalyst in Example 4 of the present invention on levofloxacin hydrochloride under different interference ion conditions. It can be seen from Figure 6 that the co-existing cations have almost no effect on the system, while Cl ^{-in the} anions will have a little negative effect. The reasons are as follows: Cl ^- will react with SO ₄ ^·- , reducing _{the SO 4} ^{·- which is the} main degrading pollutant. , Thereby inhibiting the degradation reaction.

Implementation column 5

Investigating the stability of the catalyst of the present invention includes the following steps:

(1) Collect the antibiotic-treated catalyst (CM-850) in Examples 1-4, and use suction filtration (sand core filter funnel + 0.45 μm filter membrane). It was washed three times with ultrapure water and alcohol, and then calcined at 200°C to remove the contaminants attached to the catalyst. After drying, prepare for next use.

(2) Weigh 40 mg of the regenerated catalyst (CM-850) in step (1) and add it to 100 mL of levofloxacin hydrochloride (LFX) solution with a concentration of 10 mg/L and a pH of 4.65, and magnetically stir for 30 minutes to reach Adsorption equilibrium, each add 0.05mmol permonosulfate (PMS) for degradation reaction for 60 minutes to complete the treatment of antibiotics in the water.

(3) Repeat steps (1) and (2), using a catalyst (CM-850) to degrade the levofloxacin hydrochloride (LFX) solution under the same conditions for a total of 4 times.

After the completion of each catalytic reaction, a sample of 4 mL was taken, and the obtained sample was placed in a 5 mL centrifuge tube through a 0.45 um filter membrane, and 0.1 mL of methanol quencher was added to terminate the reaction. The concentration of all samples was measured by ultraviolet at a wavelength of 292 nm to obtain the repeated degradation effect of the catalyst of the present invention on levofloxacin hydrochloride, as shown in FIG. 7.

Figure 7 is a graph showing the repeated degradation effect of the catalyst in Example 5 of the present invention on levofloxacin hydrochloride. It can be seen from Figure 7 that after four cycles of use, the catalyst of the present invention can still degrade more than 83% of levofloxacin hydrochloride without changing the phase; the reasons for the slight decrease in degradation efficiency are: (1) Cobalt has a certain degree of leaching; (2) Degradation The intermediate products may block the active sites of the catalyst. It can be seen that the catalyst of the present invention has higher activity and stability.

Implementation column 6

Investigating the degradation effect of the method of the present invention on antibiotics in different concentrations and different water bodies includes the following steps:

(1) Weigh 5 parts of the catalyst (CM-850) prepared in Example 1, each 40mg, and add them to the levofloxacin hydrochloride (LFX) solution prepared from deionized water, tap water, river water, lake water and medical wastewater. (The volume of these water bodies is 100mL, the concentration is 10mg/L, and the pH value is 4.65), magnetically stirred for 30 minutes to reach adsorption equilibrium, and each add 0.05mmol permonosulfate (PMS) for degradation reaction for 60 minutes. Complete the treatment of antibiotics in the water body.

(2) Weigh 5 parts of the catalyst (CM-850) prepared in Example 1, each 40mg, and add them to the levofloxacin hydrochloride (LFX) solution prepared from deionized water, tap water, river water, lake water and medical wastewater. (The volume of these water bodies is 100mL, the concentration is 100μg/L, and the pH value is 4.65), magnetically stirred for 30 minutes to reach adsorption equilibrium, and each add 0.05mmol permonosulfate (PMS) for degradation reaction for 60 minutes. Complete the treatment of antibiotics in the water body.

During the catalytic reaction, 4 mL was sampled every 10 minutes, and the obtained sample was placed in a 5 mL centrifuge tube through a 0.45 um filter membrane, and 0.1 mL of methanol quencher was added to terminate the reaction. The concentration of all samples was measured by ultraviolet at a wavelength of 292 nm to obtain the repeated degradation effect of the catalyst of the present invention on levofloxacin hydrochloride, as shown in FIG. 8.

Fig. 8 is a graph showing the degradation effect of the catalyst in Example 6 of the present invention on levofloxacin hydrochloride in different concentrations and different water bodies. It can be seen from Figure 8 that the system works well in actual water bodies and can be effectively degraded at a high concentration of 10 mg/L of levofloxacin hydrochloride or a low concentration of 100 μg/L.

The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions under the idea of the present invention belong to the protection scope of the present invention. It should be pointed out that for those of ordinary skill in the art, improvements and modifications made without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims (15)

1. The catalyst for activating permonosulfate to remove antibiotics in water is characterized in that it is prepared by calcining waste lithium batteries.
2. The catalyst for activating permonosulfate to remove antibiotics in water according to claim 1, wherein the calcined waste lithium battery means that the cathode material of the waste lithium battery is calcined.
3. The catalyst for activating permonosulfate to remove antibiotics in water according to claim 1 or 2, characterized in that it comprises LiCoO ₂ and Co ₃ O ₄ .
4. The catalyst for activating permonosulfate to remove antibiotics in water according to any one of claims 1 to 3, wherein the mass percentage of _{LiCoO 2 is ≥90%;}

   Preferably, the antibiotic is selected from the group consisting of levofloxacin hydrochloride, ciprofloxacin, norfloxacin, tetracycline hydrochloride, chlortetracycline, and oxytetracycline.
5. A method for preparing a catalyst for activating permonosulfate to remove antibiotics in water is characterized by comprising: calcining waste lithium batteries.
6. The method for preparing a catalyst for activating permonosulfate to remove antibiotics in water according to claim 5, characterized in that the cathode material of the waste lithium battery is calcined.
7. The method for preparing a catalyst for activating permonosulfate to remove antibiotics in water according to claim 5 or 6, characterized in that the temperature of the calcination is 550°C to 850°C; the time of the calcination is ≥ 5 hours.
8. The method for preparing a catalyst for activating permonosulfate to remove antibiotics in water according to claim 5 or 6, wherein the waste lithium battery is a waste mobile phone lithium battery;

   Preferably, the antibiotic is selected from the group consisting of levofloxacin hydrochloride, ciprofloxacin, norfloxacin, tetracycline hydrochloride, chlortetracycline, and oxytetracycline.
9. A method for removing antibiotics in water bodies, characterized in that the catalyst for activating permonosulfate to remove antibiotics in water bodies according to any one of claims 1 to 4 is used in the water body to be treated, and/or claims 5-8 The catalyst activated permonosulfate prepared by the preparation method for activating permonosulfate to remove antibiotics in water.
10. The method for removing antibiotics in water according to claim 9, characterized in that the addition amount of the catalyst is 100mg～800mg per liter of water to be treated; the addition amount of the permonosulfate is per liter 0.3 mmol～0.9 mmol of permonosulfate is added to the water to be treated.
11. The method for removing antibiotics in water according to claim 9 or 10, wherein the antibiotic is selected from the group consisting of levofloxacin hydrochloride, ciprofloxacin, norfloxacin, tetracycline hydrochloride, chlortetracycline, and oxytetracycline Group.
12. The method for removing antibiotics in a water body according to any one of claims 9-11, wherein the concentration of the antibiotic in the water body to be treated is 100 μg/L-20 mg/L; the pH value of the antibiotic water body is 3～11.
13. The method for removing antibiotics in a water body according to any one of claims 9-12, wherein the catalyst is mixed and stirred in the water body to be treated, and permonosulfate is added for degradation reaction.
14. The method for removing antibiotics in a water body according to claim 13, wherein the stirring time is 30 minutes to 60 minutes.
15. The method for removing antibiotics in a water body according to claim 13, wherein the degradation reaction time is 40 minutes to 60 minutes.

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